The present writing relates to fiber-reactive dyes, which have two heterogeneous monoazo dye radical moieties in the chemical structure thereof, and methods of preparing them.
Fiber-reactive dyes with two monoazo dye radical moieties in the molecular structure have been disclosed in U.S. Pat. No. 5,484,899 and U.S. Pat. No. 5,548,071.
The dyes according to the present writing are distinguished by an excellent fixing capacity and good wet- and light-fastness properties. Accordingly, the dyes according to this writing can solve problems occurring upon dying fibre materials at a high concentration with C.I. Reactive Red 120 compound and C.I. Reactive Yellow 84 compound, being monochlorotriazine-based reactive dyes, and with C.I. Reactive Red 195 compound and C.I. Reactive Yellow 145 compound, being difunctional reactive dyes, of which the structures are illustrated below, respectively. 
In recent, more advanced methods are required to dye fibre materials with reactive dyes in view of the quality of dyed goods and of the efficiency of dying process, which needs novel reactive dyes that have a sufficient direct-dyeing property in the dyeing process and, if not fixed on fiber, can be easily washed. Accordingly, the novel reactive dyes are strongly required that also have an excellent fastness to light, laundering, etc. while satisfying the above requirements.
Therefore, an object of the present invention is to provide reactive dyes which have a high fixing capacity and a high fiber-dye bond stability and an excellent fastness property to light and water and in which a part of dyes, having been not fixed on a fiber, can be easily washed. Furthermore, the reactive dyes in accordance with the present invention exhibit a significantly higher solubility than do the well-known dyes in which two heterogeneously or homogeneously monoazo moieties are connected to each other in a backbone, thereby show a much higher reproducing property in the exhausting dyeing and continuous dyeing.
The inventors of the present writing, after having conducted extensive research and many experiments, found that novel dyes as described in the formula 1 have a good build-up capacity as well as an excellent fastness property to light and water laundering, and do not almost leave non-fixed residual components due to an excellent adsorbing/fixing properties to have an advantage in wastewater treatment, as compared with existing monochlorotriazine-based dyes and heterogeneous difunctional dyes. The dye described herein can be used in dyeing and printing fibre materials, especially cellulosic fibre material by a general fixing method. The dye has a good absorbing/fixing rate and has excellent fastness to light and wet treatments (i.e. the dye exhibits excellent color fastness when exposed to light and/or wet treatments (e.g., with water)).
The fiber-reactive dye of the present invention is as defined in the formula 
wherein,
R11 is a lower alkyl group of C1-C4;
D is a monoazo chromophore moiety selected from the formulas 2a, 2b, 2c, 3a and 3b defined as the below; 
in the formulas 2a to 2c,
a is 0 or 1;
b is 0 or 1;
c is 0 or 1;
d is 0 or 1;
e is 0 or 1;
f is 0 or 1;
1 is the number 0 or 1;
R1 and R3 independently of one another are each hydrogen atom or C1-C4 alkyl group;
R2 is sulfo, C1-C4 alkyl, C1-C4 alkylalkoxy or carboxyl group;
R4 is sulfo, C1-C4 alkyl, C1-C4 alkylalkoxy, xe2x80x94NHCONH2 or xe2x80x94NHCOT group, wherein T is methyl, ethyl, xe2x80x94CH2CH2COOH or xe2x80x94CHxe2x95x90CHCOOH group; and
J is vinyl or CH2xe2x80x94CH2xe2x80x94Q group, wherein Q is a leaving group which can be eliminable by a base: 
in the formulas 3a and 3b,
g is 0 or 1;
his 0 or 1;
R5 is C1-C4 alkyl, C1-C4 alkoxy, hydroxyl, carbonyl, sulfo or xe2x80x94SO2J group, wherein J is the same group as defined above;
R6 is C1-C4 alkyl or carboxyl group;
R7 and R8 independently of one another are each C1-C4 alkyl group; and
R9 is hydrogen atom, carboamido, sulfomethyl, methylsulfone group;
R0 is hydrogen atom or C1-C4 alkyl group, wherein the alkyl group is substituted with halogen atom, hydroxyl, cyano, C1-C4 alkoxy, C1-C4 alkoxy carbonyl, carbonyl or sulfo group, or unsubstituted;
X is a halogen atom, hydroxyl, cyanoamine, 3-carboxypyridine-1-yl, 4-carboxypyridine-1-yl, 3-carbamoylpyridine-1-yl or an amine group optionally substituted with C1-C4 alkoxy or C1-C4 alkyl group or unsubstituted, or X is an N-heterocyclic group in which hetero atom(s) may be additionally contained; and
Z is the group of the formula 4 defined as the below. 
in the formula 4:
l is 0 or 1;
j is 0 or 1;
k is 0 or 1;
R10 is sulfo, C1-C4 alkyl, C1-C4 alkoxy or carboxyl group; and
J1 is vinyl or CH2xe2x80x94CH2xe2x80x94Q group, wherein Q is a leaving group which is eliminable by a base.
The fiber-reactive dye of the formula 1 according to the present invention has a higher reactivity, and a better fixing capacity and more excellent build-up capacity than do the existing monochlorotriazine-based compounds and vinylsulfone-based compounds.
Preferably, R is hydrogen atom, B is an ethyl group, and X is fluoride or chloride atom.
Of compounds according to the formula 1, more preferable fiber-reactive dyes are the compounds defined as in the formulas 5 to 8 below. 
wherein
A is ammonia or C1-C3 alkyl group;
X1 is fluoride or chloride atom; and
m is 0 or 1;
n is 0 or 1; and
o is 0 or 1; 
wherein
1 is the number 0 or 1;
p is 0 or 1;
q is 0 or 1;
r is 0 or 1;
s is 0 or 1;
R2 is sulfo, C1-C4 alkyl, C1-C4 alkoxy or carboxyl group;
X1 is fluoride or chloride atom; and
J is vinyl or CH2xe2x80x94CH2xe2x80x94Q group, wherein Q is a leaving group which is eliminable by a base; 
wherein
1 is the number 0 or 1;
p is 0 or 1;
q is 0 or 1;
r is 0 or 1;
s is 0 or 1;
R2 is sulfo, C1-C4 alkyl, C1-C4 alkoxy or carboxyl group;
X1 is fluoride or chloride atom; and
J is vinyl or CH2xe2x80x94CH2xe2x80x94Q group, wherein Q is a leaving group which is eliminable by a base; 
wherein
t is 0 or 1;
u is 0 or 1;
R8 is hydrogen atom or C1-C4 alkyl group, wherein the alkyl group is substituted with halogen atom, hydroxyl, cyano, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, carbonyl, sulfo group, or unsubstituted;
R9 is hydrogen atom, carboamide, sulfomethyl, methylsulfone group; and
X1 is fluoride or chloride atom.
Methods of preparing the compounds of the formula 1 are described below. Hereinafter, R11, D, R0, X and Z in the formulas 9 to 13 are the same as in the formula 1, unless stated otherwise. For convenience of explanation, the formulas 9 to 13 are first illustrated. 
in the formulas 12 and 13, D1RN corresponds to D in the formula 1, wherein D1 is a monoazo chromophore moiety; R is a substituted or unsubstituted C1-C4 alkyl group.
The compound of the formula 13, which is substantially the same as the dye defined in the formula 1, can be synthesized by one of three methods as below. It is noted that D in the formula 1 is expressed as D1RN in formula 13 for convenience of explanation.
A first method of preparing the compound of the formula 13 comprises,
A-1) the compound of the formula 11 is condensed with the compound of HNR-D1, followed by being condensed with the compound of the formula 9, to yield to the compound of the formula 12; and
A-2) the compound of the formula 12 is coupled with a diazonium salt derived from the compound of H2N-Z to yield the compound of the formula 13.
A second method of synthesizing the compound of the formula 13 comprises,
B-1) the compound of the formula 9 is coupled with a diazonium salt derived from the compound of H2N-Z to yield the compound of the formula 10; and
B-2) the compound of the formula 11 is condensed with the compound of the formula 10, followed by being condensed with HNR-D1, to yield the compound of the formula 13.
A third method of synthesizing the compound of the formula 13 comprises,
C-1) the compound of the formula 11 is condensed with the compound of the formula 9, followed by being condensed with the compound of H2N-Z to yield the compound of the formula 12; and
C-2) the compound of the formula 12 is coupled with a diazonium salt derived from the compound of H2N-Z to yield the compound of the formula 13.
Diazotization/coupling reactions in the above methods can be performed by diazotizing the compound of H2N-Z with nitrous acid at xe2x88x925xc2x0-15xc2x0 C. and pH 0.5-2, then coupling a diazonium salt thus synthesized with the compound of the formula 12 or 9 at xe2x88x925xc2x0-15xc2x0 C. and pH 0.5-2 by an acid coupler in an aqueous medium.
Both condensation reactions in each of the above methods can be performed in an organic medium, aqueous medium, or aqueous-organic medium, and preferably performed under the presence of acid coupler in the aqueous medium. Preferable examples of said acid coupler include carbonate, bicarbonate or hydroxide of alkali metal, carbonate, bicarbonate or hydroxide of alkaline earth metal, alkali metal acetate, mixture of these, tertiary amine, etc. Preferable examples of said alkali metal and alkaline earth metal include lithium, sodium, potassium, calcium, etc. and preferable examples of said tertiary amine include pyridine, triethylamine, quinoline, etc. The first condensation reaction is performed at xe2x88x9210xc2x0-40xc2x0 C., more preferably at 0xc2x0-10xc2x0 C. and pH 1.0-6.8.
The second condensation reaction is performed preferably under the presence of acid coupler in an aqueous medium at 10xc2x0-70xc2x0 C. and pH 2.0-9.0, more preferably at 20xc2x0-60xc2x0 C. and pH 2.0-8.0.
The present invention also provides a novel compound, as defined in the formula 9, which can be used as intermediate in the above methods for synthesizing the dye of the formula 1. 
wherein
R0 and R11 is the same as in the formula 1, and preferably R11 is an ethyl group.
The compounds of the formula 9 can be synthesized by the following method: 2,4-diaminobenzene-1 sulfonic acid is acylated in No. 4 amino group of two amine groups therein by a conventional way and then No. 2 amino group is substituted with C1-C4 haloalkylalcohol, followed by the resulting reactant being hydrolyzed by conventional manners to yield the compound of the formula 9.
The present invention furthermore provides a process for dyeing or printing cellulosic fibre materials with the dye of the formula 1.
The dye of the formula 1 according to the present invention is suitable for dyeing or printing all-round cellulosic fibre materials. Examples of these cellulosic fibre materials include the naturally occurring cellulosic fibres, such as cotton, linen and hemp, and pulps and regenerated celluloses; of them, the cotton is particularly preferable. The dye of the formula 1 is also suitable for dyeing or printing cellulosic blend fibres, for example, cotton/polyester, cotton/nylon blend fibres.
For dyeing processes, the amounts in which reactive dyes, like the dye of the formula 1, are used in the dyebaths can vary according to the desired depth of shade. The dye according to the present invention can be used in the amount of 0.01 to 10% by weight, preferably 0.01 to 6% by weight, based upon the dye goods.
The dye of the formula 1 according to the present invention is especially suitable for the exhaustion method.
Dyeing by the exhaustion method is in general carried out in an aqueous medium at a liquor ration of 1:2 to 1:60, preferably 1:5 to 1:20, and a temperature of 20 to 105xc2x0 C., preferably 30 to 90xc2x0 C., more preferably 40 to 80xc2x0 C.
The pad dyeing method is another suitable dyeing process for the present invention, wherein fabrics is generally picked-up in an aqueous solution, saline solution, salt solution, etc. Herein, pick-up is carried out at 20 to 150%, preferably 40 to 120%, more preferably 50 to 100%, based upon the weight of fibre material to be dyed. If appropriate in some cases, the aqueous solution contains a fixing alkali metal salt, and the fibre material after pick-up is treated with the fixing alkali metal salt. Preferable examples of said alkali metal salt include sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium borate, aqueous ammonia, sodium trichloroacetate, sodium silicate, or mixtures of these. Since alkali hydroxide and/or alkali carbonate is preferable, sodium hydroxide and/or sodium carbonate of them is more preferable.
Fixation can be also performed by steaming the picked-up fibre material at 100xc2x0 to 120xc2x0 C., particularly by action of heat, such as saturated steam. According to, so-called, cold pad-batch method, dyes are put into a padder together with alkali, then kept at a room temperature for several hours, e.g., 3 to 40 hours, to be fixed to the fibre material. After fixation, the dyeings or prints are rinsed throughout, if appropriate, by adding a dispersing agent thereto.
The dyeings and prints produced by the present invention on fibre materials have an excellent build-up capacity and levelness. Moreover, they have a high fixing capacity and the unfixed dyes can be easily removed by rinsing. Also, the difference between adsorbing and fixing capacities, i.e., the loss of soap is low. Furthermore, they have a high depth of shape, a high fibre/dye bond stability, and a good light-fastness and good wet-fastness properties, such as fastness to washing, sea water, cross-dyeing and perspiration, as well as a good fastness to pleating and fastness to ironing.